Re2O7-Catalyzed Intermolecular Dehydrative Friedel–Crafts Reaction of Aliphatic Alcohols

In this paper, we describe an operationally facile and generally applicable intermolecular dehydrative Friedel-Crafts reaction for aliphatic alcohols via Re₂O₇ catalysis in hexafluoroisopropanol (HFIP). This method obviates the need for highly corrosive Brønsted acids or strong Lewis acids; therefore, it is convenient to perform and offers improved functional group tolerance. DFT calculations suggested that the hydrogen-bonding interactions between HFIP and the perrhenate moiety significantly lowered the energetic barrier for catalytic C-O bond cleavage in aliphatic alcohols.